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US20160181096A1 - Method For Growing Germanium Epitaxial Films - Google Patents

Method For Growing Germanium Epitaxial Films Download PDF

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Publication number
US20160181096A1
US20160181096A1 US15/057,403 US201615057403A US2016181096A1 US 20160181096 A1 US20160181096 A1 US 20160181096A1 US 201615057403 A US201615057403 A US 201615057403A US 2016181096 A1 US2016181096 A1 US 2016181096A1
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Prior art keywords
germanium
approximately
silicon substrate
layer
seed layer
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US15/057,403
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Daniel N. Carothers
Craig M. Hill
Andrew TS Pomerene
Vu An Vu
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BAE Systems Information and Electronic Systems Integration Inc
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BAE Systems Information and Electronic Systems Integration Inc
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/02521—Materials
    • H01L21/02524—Group 14 semiconducting materials
    • H01L21/02532—Silicon, silicon germanium, germanium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02367—Substrates
    • H01L21/0237—Materials
    • H01L21/02373—Group 14 semiconducting materials
    • H01L21/02381—Silicon, silicon germanium, germanium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02436—Intermediate layers between substrates and deposited layers
    • H01L21/02439—Materials
    • H01L21/02441—Group 14 semiconducting materials
    • H01L21/0245—Silicon, silicon germanium, germanium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02436—Intermediate layers between substrates and deposited layers
    • H01L21/02494—Structure
    • H01L21/02496—Layer structure
    • H01L21/02502—Layer structure consisting of two layers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/0257—Doping during depositing
    • H01L21/02573—Conductivity type
    • H01L21/02579—P-type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02612—Formation types
    • H01L21/02617—Deposition types
    • H01L21/0262—Reduction or decomposition of gaseous compounds, e.g. CVD
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02612—Formation types
    • H01L21/02617—Deposition types
    • H01L21/02636—Selective deposition, e.g. simultaneous growth of mono- and non-monocrystalline semiconductor materials
    • H01L21/02639—Preparation of substrate for selective deposition
    • H01L21/02645—Seed materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02656—Special treatments
    • H01L21/02658—Pretreatments

Definitions

  • the present invention relates to epitaxial films in general, and in particular to a method for growing germanium epitaxial films on silicon substrates.
  • the first method is very selective, a germanium film only grows on a silicon layer and not on any exposed dielectric material.
  • the problem with the first method is that the resultant germanium film is very rough and has a substantially high defect density.
  • the second method is not selective at all.
  • the second method overcomes the roughness problem, the resultant germanium film occurs on an underlying silicon layer as well as an underlying dielectric layer. The growth on the underlying silicon layer is desired but the growth on the underlying dielectric layer is not.
  • the present disclosure provides an improved method for growing selective germanium epitaxial films.
  • a silicon substrate is initially preconditioned with hydrogen gas.
  • the temperature of the preconditioned silicon substrate is then decreased, and germane gas is flowed over the preconditioned silicon substrate to form an intrinsic germanium seed layer.
  • germane gas is flowed over the preconditioned silicon substrate to form an intrinsic germanium seed layer.
  • a mixture of germane and phosphine gases can be flowed over the intrinsic germanium seed layer to produce an n-doped germanium seed layer.
  • a mixture of diborane and germane gases can be flowed over the intrinsic germanium seed layer to produce a p-doped germanium seed layer.
  • a bulk germanium layer can be grown on top of the doped germanium seed layer.
  • FIG. 1 is a high-level process flow diagram of a method for growing germanium epitaxial films, in accordance with a preferred embodiment of the present invention.
  • FIG. 2 depicts a silicon substrate having a germanium epitaxial film, in accordance with a preferred embodiment of the present invention.
  • the desired smooth and highly selective germanium layer is formed using a UHV-CVD system.
  • the formation can be completed by using the following gases: hydrogen, 100% silane (SiH 4 ) 100% germane (GeH 4 ), 1% diborane (B 2 H 6 ) and 1% phosphine (PH 3 ).
  • FIG. 1 there is illustrated a high-level process flow diagram of a method for growing germanium epitaxial films, in accordance with a preferred embodiment of the present invention.
  • a silicon substrate is preconditioned with hydrogen gas at 750° C. for 60 minutes, as shown in block 11 .
  • the pressure of hydrogen is controlled at 3E ⁇ 4 mBar.
  • the temperature is ramped down from 750° C. to 350° C. in 200 minutes in vacuum 2° C. per minute, as depicted in block 12 .
  • Germane gas at 1.5E ⁇ 3 mBar is flowed over the preconditioned silicon substrate for 120 minutes, as shown in block 13 . This step initiates the layer-by-layer growth for approximately the first ten layers of detect-free single-crystal germanium can intrinsic germanium seed layer.
  • the temperature is then ramped back up from 350°°C. to 600° C. in 125 minutes in vacuum at 2° C. per minute, as depicted in block 14 .
  • a 1:3 mixture of phosphine and germane gases at 6E ⁇ 4 mBar is flowed over the intrinsic germanium seed layer for 30 minutes, as shown in block 15 .
  • This in-situ doped germanium growth step produces approximately 150 ⁇ of an n-doped germanium seed layer with a phosphorus concentration of 1E 21 atoms/cm 3 .
  • Some of the phosphorus diffuses into the underlying intrinsic germanium seed layer (from block 13 ) and reduces the stress in the underlying intrinsic germanium seed layer.
  • the stress in the germanium is initially created by the lattice mismatch between germanium and silicon from the intrinsic germanium seed layer and silicon substrate, respectively.
  • an uniform bulk single-crystal germanium film having an extremely low level of defects can be grown on top of the n-doped germanium seed layer, as depicted in block 16 .
  • germane gas at 1.5E 31 3 mBar can be flowed over the the n-doped germinanium seed layer for 480 minutes to produce approximately 1 um of an intrinsic germanium layer.
  • the bulk germanium layer may be in-situ n-doped or p-doped by injecting some phoshine or diborane, respectively, along with the germane gas.
  • the phosphine gas can be replaced by diborane gas with slightly different conditions.
  • a 1:1 mixture of diborane and germane gases at 6E ⁇ 4 mBar is flowed over the intrinsic germanium seed layer for 30 minutes in order to produce a p-doped germanium seed layer.
  • This in-situ doped germanium growth step produces approximately 150 ⁇ of a p-doped layer with a boron concentration of 5E 21 atoms/cm 3 .
  • the steps shown in blocks 13 and 15 provide an intrinsic (first) germanium seed layer and a doped (second) germanium seed layer, respectively, which are key to the growth of a smooth bulk germanium film layer.
  • the mechanism behind the steps shown in blocks 13 and 15 is that some of the phosphorus diffuses into the underlying germanium and reduces the stress in she underlying germanium. The stress is generated by the lattice mismatch between germanium and silicon. The reduction of stresses results in a smooth bulk germanium growth.
  • the smooth defect-free germanium film can be used to produce germanium photodetectors with lower dark currents than can be produced with a typical process that does not use the doped step in block 15 .
  • the disclosed method also decreases the sensitivity of germanium growth to mask size. With a typical germanium growth, the final germanium thickness varies with the size of the mask opening to the silicon substrate.
  • the overall germanium smoothness, decreased sensitivity to pattern size, and lower dark current make the disclosed method preferred for overall process integration.
  • FIG. 2 there is depicted a silicon substrate having a germanium epitaxial film, in accordance with a preferred embodiment of the present invention.
  • an intrinsic germanium seed layer 22 is grown on top of a silicon substrate 21 .
  • a bulk germanium film 24 which can be intrinsic or doped, is grown on top of a doped germanium seed layer that rests on top of intrinsic germanium seed layer 22 .
  • One conventional method for improving overall germanium smoothness and for decreasing germanium growth sensitivity to mask size is to use a silicon-germanium buffer layer.
  • the usage of a silicon buffer layer is not selective and results in germanium growth over exposed nitride and oxide regions as well as over exposed silicon regions.
  • nitride or oxide layers are used to mask regions where no germanium growth is desired, and a loss of growth selectivity requires additional processing to remove germanium from the tops of exposal nitride or oxide regions.
  • the method of the present invention does not use any silicon containing buffer layer and therefore provides a very selective germanium growth.
  • the simultaneous smooth germanium growth, low sensitivity to pattern size, and high growth selectivity are key benefits from the steps shown in blocks 12 and 13 .
  • the present invention provides an improved method for growing germanium epitaxial films.
  • the method of the present invention can be used to grow single-crystal germanium films that are very selective and yet very smooth and defect-free.
  • the improved germanium growth process allows for simpler processing and yields lower dark currents in germanium P-i-N photodiodes.

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Abstract

A method for growing germanium epitaxial films is disclosed. Initially, a silicon substrate is preconditioned with hydrogen gas. The temperature of the preconditioned silicon substrate is then decreased, and germane gas is flowed over the preconditioned silicon substrate to form an intrinsic germanium seed layer. Next, a mixture of germane and phosphine gases can be flowed over the intrinsic germanium seed layer to produce an n-doped germanium seed layer. Otherwise, a mixture of diborane and germane gases can be flowed over the intrinsic germanium seed laser to produce a p-doped germanium seed layer. At this point, a bulk germanium layer can be grown on top of the doped germanium seed layer.

Description

    CROSS-REFERENCE TO RELATED APPLICATIONS
  • This application is a divisional application of U.S. application Ser. No. 12/539,003 filed Aug. 11, 2009, the contents of which are incorporated herein by reference.
    • BACKGROUND OF THE INVENTION
  • 1. Technical Field
  • The present invention relates to epitaxial films in general, and in particular to a method for growing germanium epitaxial films on silicon substrates.
  • 2. Description of Related Art
  • There are two conventional methods for growing single-crystal germanium films on silicon substrates using ultra-high vacuum chemical vapor deposition (UHV-CVD). The first method allows a germanium film to be grown directly on top of a silicon layer, and the second method uses a silicon and silicon germanium buffer layer at the interface.
  • Since the first method is very selective, a germanium film only grows on a silicon layer and not on any exposed dielectric material. The problem with the first method is that the resultant germanium film is very rough and has a substantially high defect density. Compared with the first method, the second method is not selective at all. Thus, although the second method overcomes the roughness problem, the resultant germanium film occurs on an underlying silicon layer as well as an underlying dielectric layer. The growth on the underlying silicon layer is desired but the growth on the underlying dielectric layer is not.
  • The present disclosure provides an improved method for growing selective germanium epitaxial films.
    • SUMMARY OF THE INVENTION
  • In accordance with a preferred embodiment of the present invention, a silicon substrate is initially preconditioned with hydrogen gas. The temperature of the preconditioned silicon substrate is then decreased, and germane gas is flowed over the preconditioned silicon substrate to form an intrinsic germanium seed layer. Next, a mixture of germane and phosphine gases can be flowed over the intrinsic germanium seed layer to produce an n-doped germanium seed layer. Otherwise, a mixture of diborane and germane gases can be flowed over the intrinsic germanium seed layer to produce a p-doped germanium seed layer. At this point, a bulk germanium layer can be grown on top of the doped germanium seed layer.
  • All features and advantages of the present invention will become apparent in the following detailed written description.
    • BRIEF DESCRIPTION OF THE DRAWINGS
  • The invention itself, as well as a preferred mode of use, further objects, and advantages thereof, will best be understood by reference to the following detailed description of an illustrative embodiment when read in conjunction with the accompanying drawings, wherein:
  • FIG. 1 is a high-level process flow diagram of a method for growing germanium epitaxial films, in accordance with a preferred embodiment of the present invention; and
  • FIG. 2 depicts a silicon substrate having a germanium epitaxial film, in accordance with a preferred embodiment of the present invention.
    •  DETAILED DESCRIPTION OF A PREFERRED EMBODIMENT
  • The desired smooth and highly selective germanium layer is formed using a UHV-CVD system. The formation can be completed by using the following gases: hydrogen, 100% silane (SiH4) 100% germane (GeH4), 1% diborane (B2H6) and 1% phosphine (PH3).
  • Referring now to the drawings and in particular to FIG. 1, there is illustrated a high-level process flow diagram of a method for growing germanium epitaxial films, in accordance with a preferred embodiment of the present invention. Starting at block 10, a silicon substrate is preconditioned with hydrogen gas at 750° C. for 60 minutes, as shown in block 11. The pressure of hydrogen is controlled at 3E−4 mBar.
  • Next, the temperature is ramped down from 750° C. to 350° C. in 200 minutes in vacuum 2° C. per minute, as depicted in block 12.
  • Germane gas at 1.5E−3 mBar is flowed over the preconditioned silicon substrate for 120 minutes, as shown in block 13. This step initiates the layer-by-layer growth for approximately the first ten layers of detect-free single-crystal germanium can intrinsic germanium seed layer.
  • The temperature is then ramped back up from 350°°C. to 600° C. in 125 minutes in vacuum at 2° C. per minute, as depicted in block 14.
  • A 1:3 mixture of phosphine and germane gases at 6E−4 mBar is flowed over the intrinsic germanium seed layer for 30 minutes, as shown in block 15. This in-situ doped germanium growth step produces approximately 150 Å of an n-doped germanium seed layer with a phosphorus concentration of 1E21 atoms/cm3. Some of the phosphorus diffuses into the underlying intrinsic germanium seed layer (from block 13) and reduces the stress in the underlying intrinsic germanium seed layer. The stress in the germanium is initially created by the lattice mismatch between germanium and silicon from the intrinsic germanium seed layer and silicon substrate, respectively.
  • At this point, an uniform bulk single-crystal germanium film having an extremely low level of defects can be grown on top of the n-doped germanium seed layer, as depicted in block 16. For example, germane gas at 1.5E31 3 mBar can be flowed over the the n-doped germinanium seed layer for 480 minutes to produce approximately 1 um of an intrinsic germanium layer. If desired, the bulk germanium layer may be in-situ n-doped or p-doped by injecting some phoshine or diborane, respectively, along with the germane gas.
  • If a p-doped germanium seed layer is desired in block 15, the phosphine gas can be replaced by diborane gas with slightly different conditions. For example, a 1:1 mixture of diborane and germane gases at 6E−4 mBar is flowed over the intrinsic germanium seed layer for 30 minutes in order to produce a p-doped germanium seed layer. This in-situ doped germanium growth step produces approximately 150 Å of a p-doped layer with a boron concentration of 5E21 atoms/cm3.
  • The steps shown in blocks 13 and 15 provide an intrinsic (first) germanium seed layer and a doped (second) germanium seed layer, respectively, which are key to the growth of a smooth bulk germanium film layer. The mechanism behind the steps shown in blocks 13 and 15 is that some of the phosphorus diffuses into the underlying germanium and reduces the stress in she underlying germanium. The stress is generated by the lattice mismatch between germanium and silicon. The reduction of stresses results in a smooth bulk germanium growth.
  • The smooth defect-free germanium film can be used to produce germanium photodetectors with lower dark currents than can be produced with a typical process that does not use the doped step in block 15. The disclosed method also decreases the sensitivity of germanium growth to mask size. With a typical germanium growth, the final germanium thickness varies with the size of the mask opening to the silicon substrate. The overall germanium smoothness, decreased sensitivity to pattern size, and lower dark current make the disclosed method preferred for overall process integration.
  • With reference to FIG. 2, there is depicted a silicon substrate having a germanium epitaxial film, in accordance with a preferred embodiment of the present invention. As shown, an intrinsic germanium seed layer 22 is grown on top of a silicon substrate 21. A bulk germanium film 24, which can be intrinsic or doped, is grown on top of a doped germanium seed layer that rests on top of intrinsic germanium seed layer 22.
  • One conventional method for improving overall germanium smoothness and for decreasing germanium growth sensitivity to mask size is to use a silicon-germanium buffer layer. The usage of a silicon buffer layer, however, is not selective and results in germanium growth over exposed nitride and oxide regions as well as over exposed silicon regions. Frequently, nitride or oxide layers are used to mask regions where no germanium growth is desired, and a loss of growth selectivity requires additional processing to remove germanium from the tops of exposal nitride or oxide regions. The method of the present invention does not use any silicon containing buffer layer and therefore provides a very selective germanium growth. The simultaneous smooth germanium growth, low sensitivity to pattern size, and high growth selectivity are key benefits from the steps shown in blocks 12 and 13.
  • As has been described, the present invention provides an improved method for growing germanium epitaxial films. The method of the present invention can be used to grow single-crystal germanium films that are very selective and yet very smooth and defect-free. The improved germanium growth process allows for simpler processing and yields lower dark currents in germanium P-i-N photodiodes.
  • While the invention has been particularly shown and described with reference to a preferred embodiment, it will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the spirit and scope of the invention.

Claims (10)

What is claimed is:
1. A method for growing germanium epitaxial films, said method comprising:
preconditioning a silicon substrate with hydrogen gas at a first temperature;
decreasing said first temperature of said preconditioned silicon substrate to a second temperature;
flowing germane gas over said preconditioned silicon substrate to form an intrinsic germanium seed layer on said silicon substrate;
increasing said second temperature of said preconditioned silicon substrate to a third temperature;
flowing a mixture of diborane gas and germane gas over said intrinsic germanium seed layer to produce on p-doped germanium layer; and
growing a bulk germanium film layer on top of said p-doped germanium layer.
2. The method of claim 1, wherein said preconditioning further includes preconditioning said silicon substrate with hydrogen gas at approximately 3E31 4 mBar for approximately 60 minutes at approximately 750° C.
3. The method of claim 1, wherein said decreasing further includes decreasing said first temperature from approximately 750° C. to approximately 350° C. at approximately 2° C. per minute.
4. The method of claim 1, wherein said flowing germane gas further includes flowing germane gas over said preconditioned silicon substrate at approximately 1.5E−3 mBar for approximately 120 minutes.
5. The method of claim 1, wherein said increasing further includes increasing said second temperature of said preconditioned silicon substrate from approximately 350° C. to approximately 600° C. at approximately 2° C. per minute.
6. The method of claim 1, wherein said gas mixture includes an approximately 1:1 mixture of diborane and germane gases.
7. The method of claim 1, wherein said gas mixture is flowed over said germanium seed layer at approximately 6E−4 mBar for approximately 30 minutes.
8. The method of claim 1, wherein said bulk germanium film layer is intrinsic germanium film.
9. The method of claim 1, wherein said bulk germanium film layer is doped germanium film.
10. The method of claim 1, wherein said growing further includes flowing germane gas over said preconditioned germanium layer at approximately 1.5E−3 mBar for approximately 480 minutes.
US15/057,403 2009-08-11 2016-03-01 Method For Growing Germanium Epitaxial Films Abandoned US20160181096A1 (en)

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US9255345B2 (en) * 2013-07-26 2016-02-09 Bae Systems Information And Electronic Systems Integration Inc. Method for growing germanium/silicon—germanium superlattice
KR102045989B1 (en) * 2018-03-14 2019-11-18 한국과학기술연구원 Semiconductor device using interdiffusion and method for manufacturing the same

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